Process for rendering textiles water-repellent and product therefrom



Patented Dec. 1,

WATER-BEPEILEN T THEREFROM AND PRODUCT Walther Kaase and Ernst Waltmann,Krefeld, Germany, assignors to Heberlein Patent Corporation, New York,N. Y., a corporation of New York No Drawing. Application April 28, 1936,Serial Claims.

This invention relates to processes for producing water-repellentfibrous materials and products therefrom.

It has been suggested heretofore that water- 'repellence be produced incellulose-containing materials by treatment with esterifying agents suchas fatty acid chlorides or fatty acid anhydrides. In the execution ofthese processes, however, difiiculties have been encountered due tounfavorable reaction conditions whereby the appearance and feel of thegoods is changed. These processes also require considerable time andexpense for operation. The treatment of the material to render itwater-repellent or drop-proof is carried out ordinarily as the finaltreatment in finishing the material. It is accordingly necessary fromthe standpoint of practical mass production that the process be carriedout with considerable rapidity and be accomplished in a short periodinstead of requiring hours as heretofore.

In Germany May 2, 1935 The principal object of the present invention Iis to provide a simple process to increase waterresistance in materials,such as, for example, but without limitation, cotton, jute, linen, hempand various artificial silks and wool, in a relatively short time andwith less expense than that of the chlorides and anhydrides mentionedabove; and to produce materials having improved characteristics.

The invention accordingly comprises the novel products as well as thenovel processes and steps of processes according to which such productsare manufactured, the specific embodiments of which are describedhereinafter by way of example and in accordance with which we now preferto practice the invention.

Now We have found in accordance with our invention that treatment oftextile materials, including cellulose-containing materials and wool,with the extremely reactive isocyanic acid esters of the aliphatic,mixed aliphatic-aromatic or naphthenic series produces remarkably fineeffects, including resistance to wetting by water. For this purpose onlythe isocyanic acid esters of the series mentioned having at least 10carbon atoms for instance decylisocyanate, hexadecylisocyanate,heptadecylisocyanate, heneicosylisocyanate, octadecylisocyanate,docosylisocyanate etc. are to be employed. These substances may beprepared by well-known processes such as described in Berichte derDeutschen Chemischen Gesellschaft, 42d year, 1909, vol. 3 page 3359, cf.the article by Schroeter, Ueber Umlagerungen. In the appended claims,certain of these isocyanates have been designated by the formulaR.N=C=0, where R is an allphatic radical containing more than 10 carbonatoms. There are suitable also other isocyanates which are obtained bytransposition of saturated amines or mixtures of such saturated aminesof high molecular weight with phosgene. Such amines of high molecularweight are commercially obtainable in the way described in German PatentNo. 611,924 or French Patent No.

This transposition is effected as follows: The amine, for examplestearylamine is dissolved in hot toluene, the solution is saturated withgaseous hydrochloric acid, whereby stearylamine hydrochloride separatesout; then phosgene is passed into the mixture until solution occurs. Thereactions which occur appear to be as follows:

It is not necessary to use pure saturated airlines as mixtures ofsaturated amines of high molecular weight are well suitable, forinstance the the corresponding isocyanic-acid esters of they naphthenicacids having at least 10 carbon atoms in an aliphatic portion are alsosuitable, for example a naphthenic acid from Galician naphthacorresponding to the formula:

or a bicyclic naphthenic acid CzoHsqCOOI-I derived from Roumaniannaphtha.

There may also be employed the isocyanate obtainable from montanic acid.Montanic or hep-, tacosyl acid which corresponds to the formula:C21H55COOH, is converted into heptacosyl isocyanate in the usual way:

The statement above made that the aliphatic, mixed aliphatic-aromatic ornaphthenic acids which form part of the esters should have at least 10carbon atoms, means that there should be at least carbon atoms in thealiphatic portions of such esters. From ten carbon atoms upwardsrepresenting an even number or an uneven number of carbon atoms may beso present.

There may also be employed substances which are easily converted intothe isocyanic acid esters upon treating the textiles herein mentionedwith such substances under reaction conditions. For example we mayemploy the corresponding fatty acid azides such as palmitic acid azideCH3 (CH2) 14CO.N:

These substances become converted with elimination of nitrogen into thecorresponding isocyanic acid esters, as described in Journal flirpraktische Chemie" (2) vol. 64, page 430, cf. the article by CurtiusDellschaft.

Fatty acid azides occur as intermediate products if the way of preparingfatty acid chlorides and treating same with sodium azide is adopted, asis shown in the reactions on the preceding page of this specification.Furthermore fatty acid azides may be obtained, as is well known, bytreating fatty acid hydrazides with nitrous acid HNOz. I

In accordance with our invention it has further been found that theremay also be employed aliphatic isocyanates whose carbon chains areinterrupted by the atoms or atomic groups 0, S, N, C0.0, 0.00, NR,NR.CO, CO.NR', S02, NR'.SO2, SO2.NR' in which R. may be equal tohydrogen or may be any desired hydrocarbon radical (cf. French PatentNo. 787,785). It is known that all carboxylic acid chlorides are easilyconverted into the corresponding azides and isocyanates by the Curtiusmethod.

For the same purpose mixed aliphatic-aromatic isocyanic acid esters mayalso be used, in so far as they contain a saturated aliphatic radical ofat least 10 carbon atoms. The active --N=C=O group may in thisconnection be tied directly to the aromatic ring, 1. e., for examplewhich is 1-stearyl-oxy-phenylene-4-isocyanate.

' The aromatic radical may be hydrogenated, chlorinated, or otherwisereplaced, and the hydrogenated compound, for example, may be representedwhich is 4-carboctadecoxy tetrahydrophenyl isocyanate.

It is also possible to successfully use for waterrepellence, isocyanateswhich contain in the alkyl radical the radical of a saturated orunsaturated alcohol of the sterol series. As a technological startingmaterial for the alcohol of the sterol series there is advantageouslyemployed the sterol mixtures contained in the unsaponiflable part ofwool fat. Such mixtures may be prepared for instance in the mannerdescribed in German Patent No. 617,975. For the purpose of introductionof the active N=C=O group these alcohols are converted into esterorether-carboxylic acids and the chlorides of these esterorether-carboxylic acids are converted by the Curtius method. Thus forexample cholesterol which is an alcohol,

occurring in the unsaponiflable part of wool fat is transposed by meansof adipic acid chloride according to the following reaction:

whereby cholesterol-adipic acid ester isocyanate is formed.

The new substances mentioned are distinguished by an extremely highrapidity of action towards textile materials, particularly towardscellulose and cellulose derivatives, such as has not heretofore beenobserved in connection with any of the known methods. It is necessaryonly to bring the textile material in contact with the isocyanate, as bypassing the textile material briefly through a solution of the isocyanicacid esters in benzine or a suitable solvent and immediately thereafterit is subjected for several min utes to a high temperature to producewaterrepellence.

An action between the textile material and the treating substance occursin accordance with our invention to produce water-repellence but we donot wish to be understood to state unqualifiedly that a chemicalreaction occurs between the textile material and the chemical compoundemployed in accordance with the invention, as we are not sure that suchis the case.

One may also treat the fibers of cellulose or cellulose derivativesimmediately after the spinning process with the esters herein mentioned,to obtain water-repellence.

Impregnation of the textile materials with the esters herein mentionedmay be carried put in any desired manner with or without the use oforganic solvents or of aqueous emulsions of the esters applied bysoaking, spraying or the like. The addition of catalytic agents for thepurpose of securing the desired effect may be made, but it is notnecessary.

The water-repellent effect produced in accordance with our inventionresists domestic washing. After thorough rinsing out of the soapemployed for this purpose and drying, the textile material againmanifests water-repellent properties. It is also resistant to drycleaning.

The following are examples of embodiments of the invention as we nowprefer to carry it out. It is to be understood that these examples arenot to be construed as limiting the invention, except as indicated inthe appended claims.

Examples 1. A printed crepe, having delustered viscose rayon as warp andviscose crepe as weft, is passed through a 0.5% solution of octodecylisocyanate, CmHsvN=C=O in benzine. The time of passage is about 3seconds and the solution is at room temperature. Immediately thereafterthe so-treated material is subjected for one minute to a temperature ofC. (212 F.) and then for two minutes to a temperature of 140 C. (284F.).

2. Acetate satin having acetate silk as warp and viscose crepe as weftis sprayed with a 1% solution of heptacosyl (or montanyl) isocyanate,C21H55N=C=O, in benzine at room temperature. The solvent is evaporatedoff, and the so-treated material is subjected for two minutes to atemperature of C.

3. Dyed stockings of Bemberg silk (cuprammonium silk) are immersed in a0.3% solution of heneicosylisocyanate C21H4aN=C=0, in benzine at roomtemperature for approximately 10 seconds, then taken out and. afterevaporation of the solvent, treated for 1% minutes at 150C. 4. A cottontent cloth is passed through, a 1% solution of naphthenic isocyanate,

in benzine. After the passage which lasts about 4 seconds, the solventis evaporated off and the material is heated for 2 minutes to atemperature of 150 C.

5. A fabric, suitable for rucksacks, consisting of linen and cotton istreated with a 0.75% solution of bicyclic naphthen isocyanate,

from Roumanian naphtha in benzine in the same way as described inExample 4.

6. A viscose spun rayon fabric is treated with an 0.5% solution inbenzine of l-stearyl-oxyphenylene-4-isocyanate,

in the same way as in Example 1.

7. A poplin from mercerized cotton, suitable for rain-proof overcoats ispassed through 9 0.5% solution of octocosan-acid azide in benzine. Thesolvent is then removed by heating the fabric to about 100 C. for ashort time. Afterwards the material is exposed for two minutes to atemperature of 140.

8. A mixture of amines obtainable by hydrating train oil acids (see page1)- is converted into a mixture of isocyanie esters by means of phosgeneas above described and a 0.5% solution in benzine therefrom is prepared.A mixed fabric consisting of mercerized cotton and viscose spun rayon istreated with this solution in the same way as described in Example 7.

9. A fabric consisting of "Vistra (spun viscose rayon) is treated with a0.5% solution of cholesterol-adipic acid ester isocyanate.

in benzine as described in Example 7.

10. A wool muslin is treated with a 0.5% solution of cholesterol-adipicacid ester azide in benzine (see page 2), C21H45O.CO(CH2)4CON3, as de-.scribed in Example '7.

11. A worsted fabric is treated with a 0.5% solution of octocosan acidaz de in benzine. as described in Example 7.

12. A strong cotton fabric is passed during 3 seconds through a 0.5%solution of heptacosyl (montanyl) isocyanate, C27H5sN==C=O, in benzine,the solvent is evaporated off and the material is exposed for 2 minutesto a temperature of 150 C.

The amount of the ester deposited in all of the above examples on thematerials will naturally vary with the weight of the material. We havefound that ordinarily an amount of the ester equal to about 0.5% of thematerial being treated, is sufficient to give the effect.

The materials produced in accordance with the above examples show a highdegree of waterrepellence. They show a lesser absorption of moisture ascompared with the known processes employing fatty acid chlorides andfatty acid anhydrides. They show also greatly improved durability towarddry-cleaning, soap washing, etc. as compared with these previousmaterials. The feel and hang of the materials having waterrepellence asproduced above, is about the same as that of the untreated material.Rayons especially, when treated in accordance with the invention, showan increase in tensile strength.

The process of the invention, particularly as set forth in the specificembodiments above, may be carried out with simple apparatus atrelatively small expense and in a relatively short time.

In the claims and elsewhere where the expression cellulose-containingmaterial is employed, it is intended to 'cover fibersjyarns, fabrics orother forms of cotton, jute, linen, hemp or rayon including viscose,cuprammonium, or other pre cipitated cellulose or derivatives ofcellulose such as acetyl cellulose. Similarly, the expression textilematerial is intended to include such cellulose-containing material" andsimilar forms of wool or other animal material.

The expression isocyanate, as used in the claims, is intended to includenot only isocyanates but also azides which are capable of liberatingnitrogen to produce isocyanates and when applied to textiles and heated,for example, above C. will act thereon to produce water-repellencetherein.

Subject matter not herein claimed is claimed in our copendingapplications Serial No. 196,622, filed March 18, 1938, and Serial No.221,994, filed July 29, 1938.

While the invention has been described in detail according to thepreferred manner of carrying out the process, it will be obvious tothose skilled in the art after understanding the inven tion, thatchanges and modifications may be made therein without departing from thespirit or scope of the invention, and it is intended in the appendedclaims to cover all such changes and modifications.

What is claimed as new and desired to be secured by Letters Patent, is:

1. A process for ennobling textile material which comprises subjectingthe material to an isocyanate of the group consisting of aliphaticisocyanates, mixed aliphatic-aromatic isocyanates, and naphthenicisocyanates, which contain an aliphatic radical of at least 10 carbonatoms, and heating the material with the isocyanate to increase thewater-repellence of said material.

2. A process for ennobling textile material which comprises subjectingthe material to a naphthenic isocyanate having a naphthene radicalcontaining an aliphatic radical of at least 10 carbon atoms, and heatingthe material with the isocyanate to increase the water-repellence ofsaid material.

3. A process for ennobling textile material which comprises impregnatingthe material with an isocyanate of the group consisting of aliphaticisocyanates, mixed aliphatic-aromatic isocyanates, and naphthenicisocyanates, which contain an aliphatic radical of at least 10 carbonatoms, and heating the impregnated material for a short period at atemperature above 100 C. to increase the water-repellence of saidmaterial.

4. A process for ennobling artificial silk which comprises heating theartificial silk with an isocyanate of the group consisting of aliphaticisocyanates, mixed aliphatic-aromatic isocyanates, and naphthenicisocyanates, which contain an aliphatic radical of at least 10 carbonatoms capable of acting upon said material, for a short period at atemperature above 100 C., to increase the water-repellence of said silk.

5. A process for ennobling textile material which comprises heating thematerial with an aliphatic-aromatic isocyanate, which contains asaturated aliphatic radical of at least carbon atoms, the isocyanategroup N= C= =O being joined directly to the aromatic ring', to increasethe water-repellence of said material.

6. A textile material heated with an isocyanate to render itwater-repellent, said isocyanate being selected from the groupconsisting of aliphatic, mixed aliphatic-aromatic and naphthenicisocyanates, containing an aliphatic radical of at least 10 carbonatoms, said material having a waterrepellent property but in appearanceand feel being substantially the same as similar material untreated.

7. A textile material heated with an aliphatic isocyanate which containsan alkyl radical of at least ten carbon atoms, said material having awater-repellent property but in appearance and feel being substantiallythe same as similar material untreated.

8. A textile material heated with a naphthenic isocyanate having anaphthene radical containing an aliphatic radical of at least ten carbonatoms, said material having a water-repellent property but in appearanceand feel being substantially the same as similar material untreated.

9. A textile material heated with an aliphaticaromatic isocyanate whichcontains a saturated aliphatic radical of at least ten carbon atoms,said material having a water-repellent property but inappearance andfeel beingsubstantially the same as similar material untreated.

10. A process for treating textile material which comprises impregnatingthe material with an isocyanate of the formula RNCO in which R is anasoases aliphatic radical containing more than 10 carbo atoms, saidisocyanate being capable of actin upon said textile material to renderthe sam water-repellent, and heating the impregnate material to producewater-repellence therein.

11. A process for treating textile material whlc comprises impregnatingthe material with a isocyanate containing an aliphatic radical of eleast ten carbon atoms capable of acting upo said textile material torender the same water repellent, and heating the impregnated materii toproduce water-repellence therein.

12. A process for treating textile material whic comprises impregnatingthe. material with mixed aliphatic-aromatic isocyanate containin analiphatic radical of more than 10 carbo atoms, and capable of actingupon said textii material to render the same water-repellent, an heatingthe impregnated material to produc water-repellence therein.

13. A process for treating textile material whic comprises impregnatingthe material with mor tanyl isocyanate and heating the so impregnatematerial to render the same water-repellent.

14. A process for treating textile material whic comprises impregnatingthe material with l-ste aryl-oxy-phenylene-i-isocyanate and heating tlCERTIFICATE -OF CORRECTION.

Patent 'No. 2,505,565. December 1, 1 9h2.,

HALTHER KAASE, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction gs follows: Page 2,second column, line 5, for that portion of the formnle reading "(C H)COCl+ H01 read --(CH )L COCl+-HC1-; and that the said Letters Patentshould be read with this correction therein that the same may conform tothe record of the case in the Patent Office.

Signed and sealed this 2nd day br February, A. D. 1911.3.

(Seal) Henry Van Arsdale,

Acting Commissioner of Patents.

